ES2286341T3 - Aqueous PREPARATIONS WITH MICROENCASULATED ACTIVE PRODUCTS. - Google Patents

Abstract

Aqueous composition containing microencapsulated active compounds (I) that improve the ironing properties of textiles. An independent claim is also included for a method for improving the ironing properties of textiles by finishing the fibers, yarn or fabrics with microencapsulated silicone compounds or paraffin or polyolefin waxes.

Description

Aqueous preparations with active products microencapsulated

Field of the Invention

The invention is in the field of laundry treatment agents and refers to new preparations with microencapsulated active products, which improve ironing behavior, to a procedure for textile treatment as well as the use of active products special, microencapsulated for finishing the laundry.

State of the art

The fibers, both synthetic and natural, they have a tendency to become entangled as a result of their load static In the textile sector this is appreciated by the user as a defective touch and poor ironing ability. By this motive have been in the market for a long time now agents for the laundry softener rinse, which are called Revival agents or simply softeners. These have in common a cationic surfactant content, preferably salts of tetraalkylammonium or especially esterquats, which reduce the load static and give the laundry a more pleasant touch. Too for the problem of defective aptitude to ironing, which is put especially because folds can only smooth by several plate passes, products are known auxiliaries with which the textiles can be finished during the pretreatment of laundry or during the final treatment of the laundry In this case it is especially about compounds of silicone, paraffin waxes and polyolefin waxes. He disadvantage of these products is, however, that can only be incorporated with difficulties in aqueous preparations homogeneous and stable to storage, corresponding. Both silicone compounds and also cited waxes on the other hand have the tendency to separate, which makes the preparations have to be mixed intensely by shaking as a previous step to its application. Regardless of whether the user does not grant a purchase interest special due to such additional costs, preparations disintegrated are murky, at best; the agents transparent, clear, desired in commerce, cannot manufactured in this way or are not stable to storage.

In this regard reference will be made to the German patent application DE 2623318 A1, for which they are known capsules for use in liquid agents for the treatment of textiles, the core of the capsules being constituted by a first substance, which enlivens the finished fabrics in this way and which reduces static load, as well as by a second component, which is constituted either by a silicone oil or by a alkyl compound or by a functionalized ether compound. Capsules themselves can be formed by polycondensation on the boundary surfaces of two monomers and represent polyurethanes, polyesters or polyamides. Publication WO 01/062376 A1 refers to to microcapsules or nanocapsules, which may be treated with various active products that can be obtained according to more diverse procedures. The characteristic of these capsules is that they are chemically modified in such a way that they carry positive charges on the surface, which would accelerate the absorption on the fibers or hair. WO 01/01927 publication A1 finally discloses microcapsules that are formed by coacervation of chitosan and anionic polymers and presenting inside a matrix consisting of gel formers and by active products.

The task of the present invention consisted of therefore in providing new aqueous preparations, with the which textiles can be finished in such a way that a easy ironing ("easy ironing" effect), without them being related to this the inconveniences of the state of the art. Especially active products should be easily Incorporable and the resulting aqueous preparations should be stable to storage. Another desire was to employ those active substances that had positive effects additional in relation to the finishing of textiles.

Description of the invention

The object of the invention is constituted by aqueous preparations, for example rinse agents laundry softener, liquid washing agents or agents for the final treatment of the laundry, with active products microencapsulated, which are characterized because active products they represent substances that improve ironing behavior of textiles and which are chosen from the group consisting of waxes polyolefin waxes and waxes, the cortex of the capsules in their entirety or predominantly by chitosan.

The problem of defective formulation aptitude and low storage stability could be solved because the preparations according to the invention contain the selected active products now used in microencapsulated form. In this way transparent and stable agents can be prepared for a prolonged period of time. When the microcapsules contain, additionally, dyes, for example transparent preparations, which contain the active products in the form of clearly visible spherical structures, colored for example blue or red, which may be desirable for aesthetic reasons, since The consumer can see at a glance the presence of active auxiliary products. The microencapsulated active products extend over the fibers; at the time of ironing the capsules are broken mechanically and then release the active product spontaneously. Within the meaning of the present invention, microencapsulated active products whose shell is constituted totally or at least predominantly by chitosan will be used. Chitosan also has the tendency to spread over the fibers. Since it has maintenance and antibacterial properties,
the desired additional use is achieved with the use of chitosan microcapsules.

Active products

As active products, which improve the ironing behavior of textiles, waxes of paraffin, polyolefin waxes and mixtures thereof.

Paraffin waxes

The term waxes of paraffin saturated hydrocarbons with a sufficient length of the carbon chain, which soften or melt only to temperatures above 50, preferably above 60 ° C. Paraffin waxes can also be partially presented. oxidized, that is to say they have carboxyl groups.

polyolefin waxes

It will be understood by the denomination of waxes of polyolefin polyethylene waxes, polypropylene waxes as well as their mixtures. Appropriate representatives are those who soften or melt only at temperatures above 50, preferably above 60 ° C. They are especially preferred polyolefin waxes, such as Adalin® K product (Cognis Deutschland GmbH & Co. KG).

Waxes can be used in the form of emulsions or aqueous dispersions, where the active substance content in the range from 1 to 1 25% by weight. As other components can be used, so concomitant, small amounts of suitable emulsifiers.

Microcapsules

It will be understood by the person skilled in the art, under the expression of "microcapsules", those spherical aggregates with a diameter in the range from about 0.0001 to about 5 mm, containing at least one solid or liquid core, which be surrounded by at least one continuous coating. Said exactly, these are liquid or solid phases, finely dispersed, coated with film-forming polymers, during which the polymers precipitate on the material to be coated, after emulsion and coacervation or polymerization on the boundary surface. According to another process, molten waxes will be absorbed in a matrix ("microsponges"), which can be additionally coated with micro-particle film-forming polymers. Small, microscopic capsules, also called nanocapsules, can be dried like dust. In addition to single-core microcapsules, polynuclear aggregates, also called microspheres, are also known, containing two or more cores distributed in the continuous coating material. Microcapsules with one core or with several cores may also be surrounded by a second, a third, etc. additional coating. The coating may consist of natural, semi-synthetic or synthetic materials. Natural coating materials are, for example, gum arabic, agar-agar, agarose, maltodextrin, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides such as starch or dextran, polypeptides, protein hydrolysates, sucrose and waxes. Semisynthetic coating materials are, among others, chemically modified celluloses, especially esters and cellulose ethers, for example cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose and carboxymethyl cellulose, as well as starch derivatives, especially ethers and starch esters. Synthetic coating materials are,
for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

Examples of microcapsules, of the prior art, are the following commercial products (the corresponding coating material has been given in brackets): Hallcrest Microcapsules (gelatins, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec Millicapseln (alginic acid, agar-agar), Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar-agar) and Kuhs Probiol Nanospheres (phospholipids) as well as Primaspheres and Primasponges (chitosan), chitosan) Primasys (phospholipids).

As already indicated, the use special is the use of active products microencapsulated, whose envelope is formed, at least in part, by chitosan. Chitosan microcapsules and procedures in order to obtain them, they constitute the object of patent applications of the applicant [WO 01/01926, WO 01/01927, WO 01/01928, WO 01/01929]. The microcapsules with average diameters in the range from 0.0001 to 5, preferably from 0.001 to 0.5 and, especially, from 0.005 to 0.1 mm, which are constituted by a covering membrane and by a matrix, which contains the active products, can be obtained, for example, yes

(a1)

be prepare a matrix from the gel formers, of the chitosans and active products,

(a2)

in if necessary, the matrix is dispersed in an oil phase,

(a3)

be treat the matrix, dispersed, with aqueous polymer solutions anionic and, if necessary, the phase is eliminated here oilseed;

or

(b1)

be prepare a matrix from the gel formers, of the anionic polymers and active products,

(b2)

in if necessary, the matrix is dispersed in an oil phase,

(b3)

be treat the matrix, dispersed, with aqueous solutions of chitosans and, if necessary, the oil phase is eliminated here;

or

(c1)

be they prepare aqueous preparations of the active product with bodies oilseeds in the presence of emulsifiers to give emulsions oil-in-water (O / W),

(c2)

be treat emulsions, obtained in this way, with solutions aqueous anionic polymers,

(c3)

the matrix, obtained in this way, contacts solutions aqueous chitosans and

(c4)

the encapsulated products, obtained in this way, are separated from the aqueous phase.

Gel Formers

As gel formers will be taken in consideration, in the sense of the invention, preferably those products, which show the property of forming gels in aqueous solution at temperatures above 40 ° C. Typical examples in this respect they are heteropolysaccharides and proteins. How thermoregulatory heteropolysaccharides come into consideration preferably agarose, which may be in the form of agar-agar, obtainable from red algae even together with up to 30% by weight of agaropectins not gel formers The main components of agarose are linear polysaccharides consisting of D-galactose Y 3,6-anhydro-L-galactose,  that are linked alternately in a way β-1,3- and β-1,4-glycosidic. The heteropolysaccharides preferably have a molecular weight in the range from 110,000 to 160,000 and are colorless and tasteless As alternatives pectins come into consideration, Xanthan (including xanthan gum) as well as their mixtures. They are also preferred those types that form gels still in solution 1% aqueous by weight, which do not melt below 80 ° C and which solidify again above 40 ° C. Among the group of thermoregulatory proteins can be cited, so Example, the various types of jellies.

Chitosans

Chitosans represent biopolymers and They belong to the group of hydrocolloids. From the point of visit chemical is about partially deacetylated chitins with weights molecular molecules, which contain the monomer units -idealized- following:

one

Contrary to what happens in most hydrocolloids, which are negatively charged in the field of biological pH values, chitosans represent, under these conditions, cationic biopolymers. Positively charged chitosans can interact with charged surfaces with the opposite sign and, therefore, are used in cosmetic agents for hair and body care as well as in pharmaceutical preparations). To obtain the chitosans, chitin is used, preferably from shellfish shells, which are available in large quantities as a cheap raw material. Usually, chitin is deproteinized, in this case, according to a procedure, which has been described for the first time by Hackmann et al ., By adding bases, it is demineralized by the addition of mineral acids and finally deacetylated by adding strong bases, the molecular weight can be distributed within a broad spectrum. Preferably, those types having an average molecular weight of 10,000 to 500,000 or 800,000 to 1,200,000 Daltons and / or a viscosity according to Brookfield (1% by weight in glycolic acid) below 5,000 mPas, a degree of deacetylation in the range from 80 to 88% and an ash content less than 0.3% by weight. In order to improve water solubility, chitosans are used, as a rule, in the form of their salts, preferably as glycolate.

Oil phase

The matrix can optionally be dispersed in an oil phase as a previous step to membrane formation. As oils come into consideration, for this purpose, by example, Guerbet alcohols based on fatty alcohols with 6 up to 18, preferably 8 to 10 carbon atoms, esters of linear fatty acids with 6 to 22 carbon atoms with alcohols linear fatty acids with 6 to 22 carbon atoms, acid esters branched carboxylics with 6 to 13 carbon atoms with alcohols linear fats with 6 to 22 carbon atoms, such as, for example the myristyl myristate, myristyl palmitate, the myristyl stearate, myristyl isostearate, oleate myristyl, myristyl behenate, myristyl erucate, Cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, behenate cetyl, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, isostearate of stearyl, stearyl oleate, stearyl behenate, stearyl belching, isostearyl myristate, palmitate isostearyl, isostearyl stearate, isostearate isostearyl, isostearyl oleate, behenate isostearyl, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, isostearate oleyl, oleyl oleate, oleyl behenate, erucate oleyl, behenyl myristate, behenyl palmitate, Behenyl Stearate, Behenyl Isostearate, Oleate Behenyl, Behenyl Behenate, Behenyl Erucate, Erucilo myristate, erucilo palmitate, stearate erucilo, erucilo isostearate, erucilo oleate, Erucilo behenate and belching erucate. In addition, they are suitable esters of linear fatty acids with 6 to 22 carbon atoms with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear, fatty alcohols or branched, with 6 to 22 carbon atoms, especially malate of dioctyl, esters of linear and / or branched fatty acids with polyvalent alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and / or Guerbet alcohols, triglycerides a fatty acid base with 6 to 10 carbon atoms, liquid mixtures of mono- / di- / triglycerides based on fatty acids with 6 to 18 carbon atoms, esters of fatty alcohols with 6 to 22 atoms  of carbon and / or alcohols of Guerbet with carboxylic acids aromatic, especially benzoic acid, acid esters dicarboxylic with 2 to 12 carbon atoms with alcohols linear or branched, with 1 to 22 carbon atoms, or polyols with 2 to 10 carbon atoms and 2 to 6 groups hydroxyl, vegetable oils, branched primary alcohols, substituted cyclohexanes, carbonates of fatty alcohols with 6 up to 22 carbon atoms, linear and branched, carbonates of Guerbet, esters of benzoic acid with alcohols, linear and / or branched, with 6 to 22 carbon atoms (for example Finsolv® TN), linear or branched dialkyl ethers, symmetric or asymmetric, with 6 to 22 carbon atoms per alkyl group, Ring opening products of epoxidized acid esters fatty with polyols, silicone oils and / or hydrocarbons aliphatic or naphthenic such as, for example, squalane, squalene or dialkylcyclohexanes.

Anionic polymers

Anionic polymers have the task of form membranes with chitosans. For this purpose they are suitable, preferably, alginic acid salts. Acid Alginic consists of a mixture of polysaccharides that contain carboxyl groups with the idealized monomer component next:

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2

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The average molecular weight of alginic acid or well of the alginates is in the range from 150,000 Up to 250,000 In this case they should be understood as acid salts alginic both its products of complete neutralization and also its partial neutralization products, especially the alkaline salts and among these preferably sodium alginate ("algina") as well as ammonium and metal salts alkaline earth. Alginates are especially preferred mixed, such as, for example, sodium / magnesium alginates or sodium / calcium alginates. In an alternative way of embodiment of the invention come into consideration for this purpose however even anionic derivatives of chitosan, such as, for example, carboxylation products and, before Everything, succinylation products. Alternatively also poly (meth) acrylates with average molecular weights in the range from 5,000 to 50,000 Dalton as well as the different carboxymethyl celluloses. Instead of anionic polymers can also be used surfactants low molecular weight anionic or inorganic salts, for coating membrane formation, such as, for example, pyrophosphates

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Emulsifiers

As emulsifiers come into consideration, for For example, non-ionogenic surfactants belonging to at least one of the following groups:

?

addition products from 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of oxide propylene on linear fatty alcohols with 8 to 22 atoms of carbon, on fatty acids with 12 to 22 carbon atoms, on alkylphenols with 8 to 15 carbon atoms in the group alkyl as well as alkylamines with 8 to 22 carbon atoms in the alkyl moiety;

?

rent- and / or alkenyl oligoglycosides with 8 to 22 carbon atoms in the rest alkyla and its ethoxylated analogs:

?

addition products from 1 to 15 moles of ethylene oxide over castor oil and / or oil hardened castor;

?

addition products from 15 to 60 moles of ethylene oxide over castor oil and / or oil hardened castor;

?

partial glycerin esters and / or sorbitan with unsaturated, linear or saturated, branched, with 12 to 22 carbon atoms and / or acids hydroxycarboxylic acids with 3 to 18 carbon atoms as well as their adducts with 1 to 30 moles of ethylene oxide;

?

partial esters of polyglycerin (medium degree of self-condensation 2 to 8), polyethylene glycol (average molecular weight 400 to 5,000), trimethylolpropane, pentaerythrite, saccharic alcohols (for example sorbitol), alkylglucosides (for example methylglucoside, butylglucoside, laurylglucoside) as well as polyglycosides (for cellulose example) with saturated and / or unsaturated fatty acids, linear or branched, with 12 to 22 carbon atoms and / or acids hydroxycarboxylic acids with 3 to 18 carbon atoms as well as their adducts with 1 to 30 moles of ethylene oxide;

?

mixed pentaerythrite esters, of fatty acids, citric acid and fatty alcohols and / or esters mixed fatty acids with 6 to 22 carbon atoms, methylglucose and polyols, preferably glycerin or polyglycerin,

?

mono-, di- and de phosphates trialkyl such as mono-, di- and / or alkyl tri-PEG-phosphates and their you go out;

?

lanolin alcohols;

?

copolymers of polysiloxane-polyalkyl polyether or well corresponding derivatives;

?

block copolymers, for example Dipolyhydroxystearate polyethylene glycol-30;

?

polymer emulsifiers, by example types of Pemulen (TR-1, TR-2) from Goodrich;

?

polyalkylene glycols as well how

?

glycerin carbonate.

To obtain the microcapsules, usually prepare an aqueous solution from 1 to 10, preferably 2 to 5% by weight of the gel former, preferably of the agar-agar and it is heated under reflux. At boiling temperature, preferably at 80 up to 100 ° C, a second aqueous solution is added, containing the chitosan in amounts from 0.1 to 2, preferably from 0.25 to 0.5% by weight and active products in amounts from 0.1 to 25 and, especially, from 0.25 up to 10% by weight; This mixture is called matrix. The load of the microcapsules with the active products can be assumed both, equally, from 0.1 to 25% by weight based on weight of the capsule. If desired, they can be added at this time. also water insoluble components, for example pigments inorganic, for adjusting viscosity, adding these, as a rule, in the form of aqueous dispersions or aqueous / alcohol dispersions. For the emulsion or the dispersion of active products can be useful, in addition, add to the matrix emulsifiers and / or solubilizers. After obtaining the matrix from gel formers, chitosans and the active products can be dispersed in a very fine way the matrix optionally in an oil phase, under strong shear to form particles as small as possible during the subsequent encapsulation. In this case it has been revealed as especially advantageous to heat the matrix at temperatures in the range from 40 to 60 ° C, while the Oil phase is cooled to 10 to 20 ° C. In the last stage, which it is mandatory now again, encapsulation is carried out proper, that is the formation of the membrane of coating by contacting the chitosan in the matrix with anionic polymers. For this it is advisable to try the matrix, dispersed if necessary in the oil phase, at a temperature in the range from 40 to 100, preferably from 50 to 60 ° C, with an aqueous solution of the anionic polymer about 1 to 50 and, preferably, from 10 to 15% by weight and in this case -in necessary case - simultaneous or subsequent phase elimination oilseed The aqueous preparations, which result in this case, they have, as a rule, a microcapsule content in the range from 1 to 10% by weight. In some cases it may be advantageous that the solution of the polymers contains other components, for example emulsifiers or agents for conservation After filtration microcapsules are obtained, which they have, on average, a diameter in the range of, preferably, about 1 mm. It is advisable to sift the capsules to ensure such a homogeneous size distribution as possible. The microcapsules, obtained in this way, can submit an arbitrary form within the scope of the conditions of the obtaining however are preferably about spherical shape Alternatively, polymers can be used. anionic also for obtaining the matrix and can be taken to perform encapsulation with chitosans.

In an alternative procedure it is prepared, in first, an emulsion of oil-in-water to obtain the microcapsules, according to the invention, which contain, in addition to the oil body, water and active products, a active amount of emulsifier. To obtain the matrix, combine this preparation, under vivid agitation, with an amount corresponding of an aqueous solution of anionic polymer. The membrane formation is carried out by adding the solution Chitosan The whole process takes place preferably in the slightly acidic range at pH = 3 to 4. In case pH adjustment is necessary by adding mineral acids After the formation of the membrane, the pH value from 5 to 6, for example by adding triethanolamine or other base. In this case there is an increase of the viscosity that can be further enhanced by the addition of other thickening agents, such as for example polysaccharides, especially xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethyl celluloses and hydroxyethyl celluloses, monoesters and polyethylene glycol diesters with high acid molecular weight fatty, polyacrylates, polyacrylamides and the like. Then the microcapsules are separated from the aqueous phase for example by decantation, filtration or centrifugation.

Aqueous preparations

Usually the preparations may contain microencapsulated active products selected in quantities from 0.1 to 10, preferably from 1 to 8 and, especially, from 2 to 5% by weight -referred to the agent-. In the simplest case agents are constituted by solutions aqueous, containing only the microcapsules and, in case given, other thickening agents. This happens for example in the case of the agents for the final treatment of laundry type the auxiliary agents for ironing, in which the wash immediately before ironing.

In other cases, that is in the agents of revival or in the case of liquid washing agents, the preparations may contain, above all, also surfactants anionic, nonionic, cationic and / or amphoteric or Zwitterionic

Anionic surfactants

Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerine ether sulfonates, α-methylestersulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, ether sulfates glycerin, mixed hydroxyether sulfates, monoglyceride (ether) sulfates, amido (ether) sulfates of fatty acids, mono- and dialkylsulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as for example lactylates of acyl, acyl tartrates, acyl glutamates and aspartates of acyl, alkyl oligoglycosides sulfates, fatty acid condensates of protein (especially wheat-based plant products) and alkyl (ether) phosphates. As for the surfactants anionics contain polyglycol ether chains, these can present a conventional homolog distribution, but without However, preferably narrow. They will preferably be used alkylbenzenesulfonates, alkyl sulfates, soaps, alkanesulfonates, olefinsulfonates, methyl estersulfonates as well as mixtures thereof.

alkylbenzenesulfonates

Preferred alkylbenzenesulfonates follow the formula (I),

(I) R 1 -Ph-SO 3 X

in which R1 means a branched alkyl moiety, preferably, however, linear, with 10 to 18 carbon atoms, Ph means a phenyl moiety and X means an alkali metal and / or an alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucamonium. They are especially suitable, among them, dodecylbenzenesulfonate, tetradecylbenzenesulfonate, hexadecylbenzenesulfonate as well as their industrial mixtures in the form of salts of sodium.

Alkyl- and / or alkenyl sulfates

They should be understood as renting and / or alkenyl sulfates, which are also often referred to as sulfates of fatty alcohols, sulfated products of primary and / or secondary alcohols, which preferably follow in formula (II),

(II) R 2 O-SO 3 X

in which R2 means a linear and branched alkyl and / or alkenyl moiety, aliphatic, with 6 up to 22, preferably with 12 to 18 carbon atoms and X means an alkali metal and / or an alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucamonium. Typical examples of alkyl sulfates, which may find application in the sense of invention, are the sulfated products of capronic alcohol, of caprylic alcohol, caprinic alcohol, alcohol 2-ethylhexyl, lauryl alcohol, alcohol myristyl, cetyl alcohol, palmolethyl alcohol, stearyl alcohol, isostearyl alcohol, alcohol oleyl, elaidyl alcohol, petroselinyl alcohol, arachidic alcohol, gadoleyl alcohol, behenyl alcohol and of the erucilic alcohol as well as its industrial mixtures, which can be obtained by high pressure hydrogenation of industrial fractions of methyl esters or aldehydes from the oxosynthesis of Roelen. Sulfated products they can preferably be used in the form of their alkaline salts and, especially, of its sodium salts. They are especially preferred alkyl sulfates based on tallow fatty alcohols with 16/18 carbon atoms or vegetable fatty alcohols with a comparable carbon chain distribution, in the form of its sodium salts In the case of branched primary alcohols, these are constituted by oxoalcohols, such as those that can obtained for example by reaction of carbon monoxide and hydrogen on olefins in alpha position according to the procedure of Shop Such mixtures of alcohols can be purchased commercially under the trade names Dobanol® or Neodol®. Mixtures of Suitable alcohols are Dobanol 91®, 23®, 25®, 45®. Other possibility is constituted by oxoalcohols, such as those obtained according to the oxo, classical procedure of the Enichema firm or  well of the firm Condea by the addition of carbon monoxide and hydrogen on olefins These mixtures of alcohols are constituted by a mixture of strongly branched alcohols. Such mixtures of alcohols can be purchased commercially under the trade name Lial®. Suitable mixtures of alcohols are Lial 91®, 111®, 123®, 125®, 145®.

Soaps

Soaps means salts of acids fats of the formula (III),

(III) R3CO-OX

where R 3 CO means a acyl residue, linear or branched, saturated or unsaturated with 6 to 22 and preferably with 12 to 18 carbon atoms and X means, in turn, an alkali metal and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Typical examples are sodium salts, of potassium, magnesium, ammonium and triethanolammonium acid capronic, caprylic acid, acid 2-ethylhexanoic acid, caprinic acid, acid lauric, isotridecanoic acid, myristic acid, acid palmitic, palmoleic acid, stearic acid, acid isostearic, oleic acid, elaidinic acid, acid petroselinic, linoleic acid, linolenic acid, acid elaeoestearic acid, ricinoleic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid as well as its industrial mixtures. Preferably acids will be used Coconut or palm kernel fatty acids in the form of sodium salts or of potassium.

Nonionic Surfactants

Typical examples of nonionic surfactants are polyglycol ethers of fatty alcohols, alkylphenol polyglycol ethers, polyglycol esters of fatty acids, amido polyglycol ethers of acids fatty, polyglycol ethers of fatty amines, triglycerides alkoxylated, mixed or formal mixed ethers, alkyl (en) iloligoglycosides, Hydrolyzed fatty acid N-alkylglucamides of protein (especially wheat-based plant products), polyol fatty acid esters, saccharic esters, esters of sorbitan, polysorbates and aminoxides. As long as the nonionic surfactants contain polyglycol ether chains, these may present a distribution of conventional counterparts, preferably, however, a distribution of homologues narrow. Preferably polyglycol ethers of fatty alcohols, lower alkyl esters of fatty acids alkoxylated or alkyl oligoglycosides.

Polyglycol ethers of fatty alcohols

Polyglycol ethers of fatty alcohols, preferred, continue in formula (IV),

(IV) R 4 O (CH 2 CHR 5 O) n 1 H

in which R 4 means a alkyl and / or alkenyl moiety, linear or branched, with 6 to 22, preferably with 12 to 18 carbon atoms, R 5 means hydrogen or methyl and n1 means numbers from 1 to 20. Typical examples are addition products of, on average, 1 up to 20 and, preferably, from 5 to 10 moles of oxide of ethylene and / or propylene oxide on capronic alcohol, alcohol Caprylic, 2-ethylhexyl alcohol, alcohol Goat, lauryl alcohol, isotridecyl alcohol, alcohol myristyl, cetyl alcohol, palmoleyl alcohol, alcohol Stearyl, isostearyl alcohol, oleyl alcohol, alcohol elaidyl, petroselinyl alcohol, linolic alcohol, alcohol linolenyl, elaewestaryl alcohol, arachidic alcohol, alcohol Gadoleil, Behenyl Alcohol, Erucyl Alcohol and Alcohol Brasidilic as well as its industrial mixtures. Are especially Preferred are the addition products of 3, 5 or 7 moles of oxide of ethylene over coconut fatty alcohols Industrial

esters of alkoxylated fatty acids

As lower alkyl esters of acids alkoxylated fatty acids the surfactants of the formula (V),

(V) R 6 CO- (OCH 2 CHR 7) n 2 OR 8

in which R 6 CO means a acyl residue, linear or branched, saturated and / or unsaturated with 6 up to 22 carbon atoms, R 7 means hydrogen or methyl, R 8 means alkyl radicals, linear or branched, with 1 to 4 carbon atoms and n2 means numbers from 1 to 20. Examples Typical are occlusion products, in terms of their formula, of, on average, 1 to 20 and preferably 5 to 10 moles of ethylene oxide and / or propylene oxide in the esters of methyl, ethyl, propyl, isopropyl, butyl and tert-butyl of capronic acid, caprylic acid, acid 2-ethylhexanoic acid, caprinic acid, acid lauric, isotridecanoic acid, myristic acid, acid palmitic, palmoleic acid, stearic acid, acid isostearic, oleic acid, elaidinic acid, acid petroselinic, linoleic acid, linolenic acid, acid elaeoesteáric, arachidic acid, gadoleic acid, Behenic acid and erucic acid as well as mixtures thereof Industrial Usually the obtaining of the products by inserting alkylene oxides in the bond carbonyl ester in the presence of special catalysts such as, for example, calcined hydrotalcite. They are especially preferred reaction products of, on average, 5 to 10 moles of ethylene oxide in the ester bond of the methyl esters of the coconut fatty acids Industrial

Alkyl- and / or alkenyl oligoglycosides

The alkyl- and alkenyl oligoglycosides, which they also represent preferred nonionic surfactants, usually follow the formula (VI)

(VI) R 9 O- [G] p

in which R 9 means a alkyl and / or alkenyl moiety with 4 to 22 carbon atoms, G means a saccharic moiety with 5 or 6 carbon atoms and p means numbers from 1 to 10. These can be obtained according to procedures of the preparative organic chemistry branch. The alkyl- and / or alkenyl oligoglycosides can be derived from aldoses or either of ketoses with 5 or 6 carbon atoms, preferably of the glucose. Preferred alkyl- and / or alkenyl oligoglycosides are, therefore, alkyl- and / or alkenyl oligoglycosides. The index Numeric p in the general formula (VI) indicates the degree of oligomerization (DP), that is, the distribution of monoglycosides and oligoglycosides and represents a number between 1 and 10. While p in a given compound has to always be an integer and, in this case, first of all, take p = 1 to 6 values, the p value for a determined alkyl oligoglycoside is a numerical magnitude, analytically determined, that, most of the time, It represents a fractional number. They will preferably be used alkyl- and / or alkenyl oligoglycosides with an average degree of oligomerization p from 1.1 to 3.0. From the point of view of industrial applications are preferred those rent- and / or alkenyl oligoglycosides whose oligomerization degree is less than 1.7 and that is included, especially, between 1.2 and 1.4. The alkyl or alkenyl R 9 moiety may be derived from primary alcohols with 4 to 11, preferably with 8 to 10 carbon atoms Typical examples are butanol, capronic alcohol, caprylic alcohol, caprylic alcohol and undecyl alcohol as well as their industrial mixtures, such as those obtained, for example, in the hydrogenation of methyl esters of industrial fatty acids or during the hydrogenation of the aldehydes in the Roelen oxosynthesis. Alkyl oligoglycosides are preferred with a chain length with 8 to 10 carbon atoms (DP = 1 up to 3), which are obtained as a head product during distillation separation of industrial coconut fatty alcohols with 8 to 18 carbon atoms and that may be impurified with a proportion less than 6% by weight of alcohol with 12 atoms carbon, as well as oxoalcohols-based alkyl oligoglycosides industrial with 9/11 carbon atoms (DP = 1 to 3). The rest alkyl or alkenyl R 9 can be derived in addition to primary alcohols with 12 to 22, preferably with 12 to 14 carbon atoms Typical examples are lauryl alcohol, alcohol myristyl, cetyl alcohol, palmoleyl alcohol, alcohol Stearyl, isostearyl alcohol, oleyl alcohol, alcohol elaidyl, petroselinyl alcohol, arachidic alcohol, alcohol gadoleil, behenyl alcohol, belching alcohol, alcohol Brazil, as well as its industrial mixtures, which can Obtained as described above. Preferred are alkyl oligoglycosides based on coconut alcohols hardened with 12/14 carbon atoms with a DP of 1 to 3.

Cationic surfactants

Typical examples of cationic surfactants they are, especially tetraalkylammonium compounds such as, for example, dimethyldiestearylammonium chloride or hydroxyethyl hydroxycetyl dimonium (Dehyquart E) or esterquats, which they are, typically, the components of the agents of revival. In This case is, for example, quaternized salts of fatty acid triethanolamine of the formula (VII),

3

wherein R 10 CO means an acyl moiety with 6 to 22 carbon atoms, R 11 and R 12 mean, independently of each other, hydrogen or R 10 CO, R 2 11 means an alkyl moiety with 1 to 4 carbon atoms or a group (CH 2 CH 2 O) m4
H, m1, m2 and m3 mean in sum 0 or numbers from 1 to 12, m4 means numbers from 1 to 12 and Y means halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats, which may find application within the meaning of the invention, are products based on capronic acid, caprylic acid, caprinic acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidinic acid , arachidic acid, behenic acid and erucic acid as well as their industrial mixtures, such as those formed, for example, in the pressure dissociation of natural fats and oils. Preferably, coconut fatty acids, industrial, with 12/18 carbon atoms and, especially, partially hardened, tallow or palm fatty acids with 16/18 carbon atoms as well as 16/18 fatty acid fractions will be used. carbon atoms rich in elaidinic acid. To obtain the quaternized esters, fatty acids and triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1. As regards the industrial application properties of the esterquats, a mixing ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proved to be especially advantageous. . Preferred esters represent industrial mixtures of mono-, di- and tri-esters with an average degree of esterification of 1.5 to 1.9 and are derived from tallow or palm industrial fatty acids with 16/18 industrial carbon atoms ( iodine index 0 to 40). From the point of view of industrial application, quaternized salts of fatty acid triethanolamine esters of the formula (VII) have been found to be especially advantageous, in which R 10 CO means an acyl moiety with 16 to 18 atoms carbon, R 11 means R 10 CO, R 12 means hydrogen, R 13 means a methyl group, m1, m2 and m3 means 0 and Y means methyl sulfate.

Together with the quaternized salts of triethanolamine fatty acids come into consideration by way of esterquats, in addition, also, quaternized salts of esters of acids with diethanolalkylamines of the formula (VIII),

4

where R 14 CO means a acyl moiety with 6 to 22 carbon atoms, R 15 means hydrogen or R 14 CO, R 16 and R 17 mean, independently of each other, alkyl moieties with 1 to 4 atoms of carbon, m5 and m6 in sum mean 0 or numbers from 1 to 12 and Y means halide, alkyl sulfate or alkyl phosphate. How another group of suitable esterquats can be cited, finally, the quaternized salts of fatty acid esters cited with 1,2-dihydroxypropylialkylamines of the formula (IX),

5

where R 18 CO means a acyl moiety with 6 to 22 carbon atoms, R 19 means hydrogen or R 18 CO, R 20, R 21 and R 22 mean, independently of each other, alkyl moieties with 1 to 4 atoms of carbon, m7 and m8 in sum mean 0 or numbers from 1 to 12 and X means, again, halide, alkyl sulfate or phosphate of I rent. Finally they come into consideration, by way of esterquats, also, products in which the ester group is replaced by a amide group and which are preferably based on diethylenetriamines, which follow the formula (X) next,

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6

wherein R 23 CO means a acyl moiety with 6 to 22 carbon atoms, R 24 means hydrogen or R 23 CO, R 25 and R 26 mean, independently of each other, alkyl moieties with 1 to 4 atoms of carbon and Y means, again, halide, alkyl sulfate or alkyl phosphate. Such amidoesterquats can be purchased at trade, for example, under the Incroquat® brand (Croda)

Amphoteric or zwitterionic surfactants

Examples of amphoteric surfactants or Suitable zwitterionics are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetains Examples of suitable alkyl betaines are represented by the carboxy alkylation products of amines secondary and, especially, tertiary, which remain in the formula (XI),

7

in which R 27 means residues alkyl and / or alkenyl with 6 to 22 carbon atoms, R 28 means hydrogen or alkyl moieties with 1 to 4 atoms of carbon, R 29 means alkyl moieties with 1 to 4 atoms of carbon, q1 means numbers from 1 to 6 and Z means a metal alkaline and / or alkaline earth or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, from hexyl dimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylmethylmethylamine,  of coconut alkyldimethylamine with 12/14 carbon atoms, of myristyldimethylamine, cetyldimethylamine, stearyl dimethylamine, stearylethylmethylamine, oleildimethylamine, tallow alkyldimethylamine with 16/18 atoms of carbon as well as its industrial mixtures. In addition, they enter consideration also the carboxy alkylation products of amidoamines, which follow the formula (XII),

8

wherein R 30 CO means a aliphatic acyl moiety with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 31 means hydrogen or alkyl moieties with 1 to 4 carbon atoms, R 32 means alkyl moieties with 1 up to 4 carbon atoms, q2 means numbers from 1 to 6, q3 means numbers from 1 to 3 and Z means, again, a alkali metal and / or alkaline earth metal or ammonium. Typical examples of reaction products of fatty acids with 6 to 22 atoms of carbon, in particular capronic acid, caprylic acid, acid caprinic, lauric acid, myristic acid, palmitic acid, acid palmoleic, stearic acid, isostearic acid, oleic acid, elaidinic acid, petroselinic acid, linoleic acid, acid linolenic acid, elaeoestearic acid, arachidic acid, acid gadoleic, behenic acid and erucic acid as well as their mixtures industrial, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which condense with sodium chloroacetate. The use of a product of condensation of N, N-dimethylaminopropylamide from coconut fatty acids with 8/18 carbon atoms with chloroacetate sodium. In addition, betaines of imidazolinium Also these substances are constituted by known products, which can be obtained for example by Cyclic condensation of 1 or 2 moles of fatty acids with polyvalent amines such as, for example, aminoethylene ethanolamine (AEEA) or diethylenetriamine. Carboxyalkylation Products corresponding represent mixtures of open chain betaines different. Typical examples are the condensation products of the fatty acids mentioned above with AEEA, preferably imidazolines based on lauric acid or also fatty acids of coconut with 12/14 carbon atoms, which are betainized, then  with chloroacetate sodium.

Thickening agents

In a preferred embodiment of the invention is desirable to provide the preparations with a viscosity so high that the microcapsules remain dispersed in a stable way, that is to say that they do not settle in the over time. It will be understood by the expression viscosity elevated therefore that rheology with which the stabilization of the microcapsules in aqueous (surfactant) phase. Usually such viscosities (determined according to Brookfield, RVT viscometer, 20ºC, spindle 1, 10 revolutions per minute) se they are above 100 and, preferably, above 500 mPas, preferably in the range from 0 to 2,000 and, especially, from 500 to 1,000 mPas. Thickeners suitable are all those products that provide the formulations a corresponding high viscosity. Preferably, however, these are polymeric compounds that these are able to establish a three-dimensional network in the aqueous preparations, in which the microcapsules Typical examples are types of Aerosil (acids hydrophilic silicic), polysaccharides, especially xanthan gum, the guar-guar, the agar-agar, the alginates and tyloses, carboxymethyl cellulose and hydroxyethyl- and hydroxypropyl cellulose, in addition to the monoesters and diesters of high molecular weight polyethylene glycol of fatty acids, polyacrylates (for example Carbopole® and pemulene types of Goodrich; Sigma Synthalene®; Keltrol types from Kelco; Sepigel types of the Seppic firm; types of signature Salcare Allied Colloids), polyacrylamides, polymers, alcohol polyvinyl and polyvinylpyrrolidone. They have revealed themselves as especially effective also bentonites, such as, for example, Bentone® Gel VS-5PC (Rheox), which are constituted by a mixture of cyclopentasiloxane, of diesteardimonium hectorite and propylene carbonate. The proportion of these thickening agents in aqueous preparations it can be between 0.1 and 5, preferably between 0.5 and 3 and, especially, between 1 and 2% by weight.

Industrial application

Two other objects of the present invention are refer to a procedure to improve behavior by ironing of textiles, in which they undergo a treatment final fibers, threads or flat textile structures with microencapsulated active products, which are chosen from the group formed by paraffin waxes and polyolefin waxes and in the which capsule bark is constituted total or predominantly by chitosan and the use of waxes paraffin and / or microencapsulated polyolefin waxes, in the which capsule bark is constituted total or predominantly by chitosan, to obtain agents for the laundry treatment.

Examples

Example one

They dissolved in a three-necked flask, of 500 ml, with stirrer and reflux coolant, at temperature  of boiling, 3 g of agar-agar in 20 ml of water. TO the mixture was then combined, within 30 minutes approximately, under vivid turmoil, first with a solution of 10 g of glycerin and 90 ml of water and then with a preparation of 2.5 g of sodium alginate in the form of a 10% aqueous solution by weight, 3 g of an aqueous wax emulsion of paraffin, 0.5 g of preservative (Phenonip®) and 0.5 g of polysorbate-20 (Tween® 20, ICI) in 64 g of Water. The matrix obtained was filtered, heated to 60 ° C and added drop by drop in a 1% by weight solution of chitosan glycolate in water To obtain the microcapsules with the same diameter the preparations were then screened.

Example 2

They dissolved in a three-necked flask, of 500 ml, with stirrer and reflux coolant, at the temperature of boil, 3 g of agar-agar in 200 ml of water. TO the mixture was then combined within 30 minutes approximately, under vivid turmoil, first with a solution of 10 g of glycerin in 90 ml of water and then with a preparation of 2.5 g of sodium alginate in the form of a 10% aqueous solution by weight, 5 g of an aqueous wax emulsion of polyolefin (Adalin® K), 0.5 g of preservative (Phenonip®) and 0.5 g of polysorbate-20 (Tween® 20, ICI) in 64 g of water. The matrix obtained was filtered, heated to 60 ° C and added dropwise to a 1% by weight solution of Chitosan glycolate in water. To obtain microcapsules of equal diameter the preparations were then screened.

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Table 1 below contains examples of formulation for a liquid washing agent (A) and for a revival (B):

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TABLE 1

9

Claims (12)

1. Aqueous preparations with microencapsulated active products, characterized in that the active products represent substances that improve the ironing behavior of textiles and are chosen from the group formed by paraffin waxes and polyolefin waxes, the bark of the capsules totally or predominantly by chitosan. 2. Preparations according to claim 1, characterized in that they are constituted by agents for the laundry rinse. 3. Preparations according to claim 1, characterized in that they consist of liquid washing agents. 4. Preparations according to claim 1, characterized in that they are constituted by agents for the final treatment of the laundry. 5. Preparations according to at least one of claims 1 to 4, characterized in that the polyolefin waxes consist of polyethylene waxes and / or polypropylene waxes. 6. Preparations according to at least one of claims 1 to 5, characterized in that the active products are present in an aqueous emulsion or dispersion. 7. Preparations according to at least one of claims 1 to 6, characterized in that they contain microcapsules with average diameters in the range from 0.0001 to 5 mm, consisting of a crust-forming membrane and a matrix containing the active products, characterized because they can be obtained by

(a1)

preparation of a matrix from gel, chitosan and active product formers,

(a2)

in given case, dispersion of the matrix in an oil phase,

(a3)

dispersed matrix treatment with aqueous solutions of anionic polymers and, where appropriate, elimination in this case of the oil phase;

or

(b1)

preparation of a matrix from gel formers, anionic polymers and active products,

(b2)

in given case, dispersion of the matrix in an oil phase,

(b3)

dispersed matrix treatment with aqueous solutions of chitosan and, where appropriate, disposal in this case of the oil phase;

or

(c1)

preparation of aqueous preparations of active products with oleaginous bodies in the presence of emulsifiers to give emulsions oil-in-water (O / W),

(c2)

emulsion treatment, obtained in this way, with aqueous polymer solutions anionic,

(c3)

matrix contact obtained in this way, with aqueous solutions of chitosan Y

(c4)

product separation encapsulated, thus obtained, from the aqueous phase.

8. Preparations according to at least one of claims 1 to 7, characterized in that the microencapsulated active products are contained in amounts from 0.1 to 10% by weight -referred to the agent-. 9. Preparations according to at least one of claims 1 to 8, characterized in that they also contain anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. 10. Preparations according to at least one of claims 1 to 9, characterized in that they contain other thickening agents. 11. Procedure to improve behavior ironing of textiles according to which they undergo a final treatment fibers, threads or flat structures textiles with microencapsulated active products, which are chosen between the group formed by paraffin waxes and waxes polyolefin, the total capsule cortex being constituted or predominantly by chitosan. 12. Use of paraffin waxes and / or microencapsulated polyolefin waxes whose capsule bark it is constituted totally or predominantly by chitosan, for the manufacture of agents for the treatment of laundry.